CN107708966B - Heat-shrinkable polyester film and package - Google Patents
Heat-shrinkable polyester film and package Download PDFInfo
- Publication number
- CN107708966B CN107708966B CN201680033264.4A CN201680033264A CN107708966B CN 107708966 B CN107708966 B CN 107708966B CN 201680033264 A CN201680033264 A CN 201680033264A CN 107708966 B CN107708966 B CN 107708966B
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- CN
- China
- Prior art keywords
- film
- shrinkage
- heat
- polyester
- shrinkable polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920006267 polyester film Polymers 0.000 title claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims description 21
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 11
- 229920001225 polyester resin Polymers 0.000 claims description 10
- 239000004645 polyester resin Substances 0.000 claims description 10
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 description 70
- 239000010410 layer Substances 0.000 description 47
- 229920005989 resin Polymers 0.000 description 42
- 239000011347 resin Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 33
- 238000011156 evaluation Methods 0.000 description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 27
- 239000012792 core layer Substances 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 238000002156 mixing Methods 0.000 description 17
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 16
- 230000008025 crystallization Effects 0.000 description 16
- 238000001125 extrusion Methods 0.000 description 16
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 14
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 11
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- 230000000052 comparative effect Effects 0.000 description 8
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 7
- 235000013361 beverage Nutrition 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 6
- 229940035437 1,3-propanediol Drugs 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000002372 labelling Methods 0.000 description 3
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
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- 229920006300 shrink film Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 2
- VVOISBSEMFDYNE-UHFFFAOYSA-N 2-propan-2-ylpropane-1,3-diol Chemical compound CC(C)C(CO)CO VVOISBSEMFDYNE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000003484 crystal nucleating agent Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
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- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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- 239000000779 smoke Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
Classifications
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Abstract
[ problem ] to provide a heat-shrinkable polyester film which has sufficient heat-shrinkable characteristics in the main shrinkage direction, i.e., the longitudinal direction, has a low heat-shrinkage rate in the width direction perpendicular to the main shrinkage direction, does not have an excessively high shrinkage stress in the main shrinkage direction, and has a small decay of the shrinkage stress, so that it has high conformability to a container to be packaged during shrinkage and is less likely to undergo relaxation. [ solution ] A heat-shrinkable polyester film which is characterized in that the film is a heat-shrinkable polyester film having a main shrinkage direction in the longitudinal direction, and (1) the hot water shrinkage ratio in the main shrinkage direction of the film when treated in hot water at 98 ℃ for 10 seconds is 40% or more and 80% or less, (2) the hot water shrinkage ratio in the direction perpendicular to the main shrinkage direction of the film when treated in hot water at 98 ℃ for 10 seconds is-5% or more and 10% or less, (3) the shrinkage stress ratio in the main shrinkage direction of the film measured under hot air at 90 ℃ is 0.6 or more and 1.0 or less, and (4) the refractive index in the main shrinkage direction of the film is 1.600 or more.
Description
Technical Field
The present invention relates to a heat-shrinkable polyester film and a package, and more particularly to: a heat-shrinkable polyester film suitable for labeling applications, bundling applications such as containers, and the like, and a heat-shrinkable polyester film which is less likely to undergo relaxation of a packaged body due to less attenuation of shrinkage stress during heat shrinkage.
Background
In recent years, stretched films (so-called heat-shrinkable films) made of a polyvinyl chloride resin, a polystyrene resin, a polyester resin, or the like have been widely used for applications such as label packaging, cap sealing, and integrated packaging that combine protection of glass bottles, PET bottles, and the like and presentation of commercial products. Among such heat-shrinkable films, polyvinyl chloride films have low heat resistance and have the following problems: hydrogen chloride gas is generated during incineration, and the hydrogen chloride gas causes dioxin. In addition, polystyrene-based films have the following problems: the ink composition is poor in solvent resistance, and it is necessary to use ink having a specific composition in printing, and to burn the ink at a high temperature, and a large amount of black smoke is generated due to offensive odor in burning. Therefore, polyester-based heat-shrinkable films having high heat resistance, easy incineration, and excellent solvent resistance are widely used as shrink labels, and their useful amount tends to increase with an increase in the flow rate of PET containers.
In addition, as a general heat-shrinkable polyester film, a film which shrinks greatly in the width direction is widely used. When used as a label film for bottles, a taping film (binding film) for bundling containers, etc., it is necessary to form a film into a ring shape and attach the film to a bottle or a container and then thermally shrink the film in the circumferential direction. Therefore, it is difficult to attach a label film or a band film, which is formed of a heat-shrinkable film heat-shrunk in the width direction, to a bottle or a container at high speed. Therefore, recently, a film which is heat-shrinkable in the longitudinal direction and can be directly wound around a bottle from a film roll and mounted is sought. The film can be mounted at high speed without the need for a center sealing step for forming and sealing the film ring, cutting, holding, or the like.
As a demand for shrink films, it is required to follow the shape of an object to be packaged during shrinking and to have a tight feeling after shrinking. In the case of a label for a beverage bottle, if the label does not follow the shape and is not tight, there is a problem that the label is rotated and is not easily opened when a consumer opens a lid of the bottle while holding a bottle body. In the case of the band application of the container, a tight processing of the shrink film is required in order to prevent the contents from overflowing and to prevent the foreign matter from being mixed.
As a method of increasing the degree of strain after the shrinkage process, it is considered to increase the shrinkage stress, but when the shrinkage stress is too high, there is a problem that the container is deformed when packed in a thin and flexible beverage bottle or a container. Further, there is a problem that the adhesive portion of the tubular label or the band film is peeled off due to a high shrinkage stress.
For example, patent document 1 describes the following heat-shrinkable film: after stretching in the longitudinal direction, the intermediate heat treatment is performed, and then the stretching in the width direction is performed, so that the maximum value of the shrinkage stress in the width shrinkage direction in hot air at 90 ℃ is large, and the attenuation of the shrinkage stress after 30 seconds is small, and it is described that the following property to the container is good, the relaxation after processing is not easily generated, and the appearance is good in the label application.
However, the method described in patent document 1 requires a large-scale facility for biaxial stretching, and thus has a problem of high cost. Further, as described above, it is difficult to mount the film shrunk in the width direction on a bottle at high speed.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5240387
Disclosure of Invention
Problems to be solved by the invention
An object of the present invention is to provide: a heat-shrinkable polyester film which has sufficient heat-shrinkable characteristics in a main shrinking direction which is a longitudinal direction, has a low heat-shrinkable rate in a width direction which is orthogonal to the main shrinking direction, has a shrinkage stress in the main shrinking direction which is not excessively high, and has a small attenuation of the shrinkage stress, and which has a high ability to follow a container as a packaged body at the time of shrinkage and is less likely to be relaxed.
Means for solving the problems
That is, the present invention includes the following configurations.
1. A heat-shrinkable polyester film characterized by satisfying the following characteristics (1) to (4) and having a main shrinkage direction as a longitudinal direction.
(1) The hot water shrinkage rate of the film in the main shrinkage direction is 40-80% when the film is treated in hot water at 98 ℃ for 10 seconds
(2) A hot water shrinkage ratio of-5% to 15% in a direction perpendicular to a main shrinkage direction when treated in hot water at 98 ℃ for 10 seconds
(3) The shrinkage stress ratio of the film in the main shrinkage direction measured under hot air at 90 ℃ is 0.6 to 1.0
Shrinkage stress ratio ═ (value of shrinkage stress after 30 seconds) ÷ (maximum value of shrinkage stress)
(4) The refractive index of the film in the main shrinkage direction is 1.600 or more
2. The heat-shrinkable polyester film according to claim 1, wherein the maximum shrinkage stress in the main shrinkage direction of the film measured with hot air at 90 ℃ is 15MPa or less.
3. The heat-shrinkable polyester film according to the above 1 or 2, characterized in that it comprises ethylene terephthalate as a main component and 1 or more kinds of monomer components capable of becoming amorphous components are contained in an amount of 10 mol% or more in the entire polyester resin component.
4. The heat-shrinkable polyester film according to any one of the above 1 to 3, wherein neopentyl glycol is used as 1 or more kinds of monomer components capable of becoming amorphous components.
5. A package obtained by covering at least a part of the outer periphery of an object to be packaged with the heat-shrinkable film according to any one of items 1 to 4 and then heat-shrinking the covered object.
ADVANTAGEOUS EFFECTS OF INVENTION
The present inventors have conducted intensive studies and, as a result, have found that: the present inventors have found that, in a single layer film obtained from a single resin or a laminated film obtained by laminating different resins, by using at least 1 layer of a polyester resin having a specific composition, shrinkage stress in a main shrinkage direction is not excessively high and the decay of the shrinkage stress is small, so that the following property to a container as a packaged body at the time of shrinkage is high and relaxation is not easily generated, and thus the present invention has been completed.
That is, according to the present invention, there can be provided: a heat-shrinkable polyester film which has sufficient heat-shrinkable characteristics in a main shrinking direction which is a longitudinal direction, has a low heat-shrinkable rate in a width direction which is orthogonal to the main shrinking direction, has a shrinkage stress in the main shrinking direction which is not excessively high, has a small shrinkage stress decay, has a high ability to follow a container which is a packaged body at the time of shrinking, and is less likely to cause relaxation. The heat-shrinkable polyester film of the present invention can be suitably used as a film for labeling a bottle or a binding film for binding a container such as a lunch, and the main shrinking direction is the longitudinal direction, so that it can be mounted very efficiently in a short time, and when it is heat-shrunk after mounting, it is insufficient in shrinkage, longitudinal shrinkage, deformation of the container are extremely small, and the shrinkage stress is attenuated little, so that it has good conformability to the container, is less likely to be loosened, and can be processed well.
Drawings
FIG. 1 shows a convenient plastic container for evaluating wrinkles of a shrunk film
FIG. 2 shows a convenient plastic container for evaluating shrinkage cavity of a film after shrinkage
Description of the reference numerals
1: lunch container
2: film(s)
3: fold of
4: lunch container
5: film(s)
Detailed Description
The structure of the heat-shrinkable polyester film of the present invention will be described in detail below.
The heat-shrinkable polyester film of the present invention has at least one layer containing 50 mol% or more of ethylene terephthalate units in 100 mol% of constituent units of a polyester. As will be described in detail later, according to the results of the study by the present inventors, it is found that when the stretch ratio of a film having at least one layer containing 50 mol% or more of ethylene terephthalate units out of 100 mol% of the constituent units of the polyester is higher than 3 times, crystallization proceeds, and therefore, the rate of attenuation of the shrinkage stress is small, and the shrinkage stress after 30 seconds from the start of shrinkage becomes high.
[ case of Single-layer film ]
In the case of a single-layer film, for the above reasons, the polyester used in the heat-shrinkable polyester film contains ethylene terephthalate units as a main component, and the ethylene terephthalate units are 50 mol% or more based on 100 mol% of the constituent units of the polyester. In order to promote crystallization during stretching in the longitudinal direction described later, the ethylene terephthalate unit is preferably at least 55 mol%, more preferably at least 60 mol%, out of 100 mol% of the constituent units of the polyester. However, when the ratio of the ethylene terephthalate unit is too high, the shrinkage is hindered by crystallization, and it is difficult to obtain a desired high shrinkage, and therefore, the upper limit of the ethylene terephthalate unit is preferably 70% or less.
Examples of the other dicarboxylic acid component constituting the polyester of the present invention include aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, and phthalic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid, and alicyclic dicarboxylic acids.
When an aliphatic dicarboxylic acid (for example, adipic acid, sebacic acid, decanedicarboxylic acid, etc.) is contained in the polyester, the content is preferably less than 3 mol% (based on 100 mol% of the dicarboxylic acid component).
Further, it is preferable that the polyester does not contain a tricarboxylic acid or more (for example, trimellitic acid, pyromellitic acid, anhydride thereof, or the like). It is difficult to achieve a desired high shrinkage ratio in a heat-shrinkable polyester film obtained using a polyester containing such a polycarboxylic acid.
Examples of the diol component constituting the polyester include aliphatic diols such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol and hexanediol, alicyclic diols such as 1, 4-cyclohexanedimethanol, and aromatic diols such as bisphenol a.
In addition, in the polyester, the total of 1 or more monomer components that can become amorphous components in 100 mol% of the polyol component or 100 mol% of the polycarboxylic acid component in the entire polyester resin is 2% or more, preferably 3% or more, more preferably 4% or more, and particularly preferably 5% or more. Further, when the amount of the monomer component capable of forming an amorphous component is large, crystallization during stretching in the longitudinal direction does not sufficiently proceed, and therefore, the upper limit is preferably 20 mol%.
Examples of the monomer that can be used as the amorphous component include neopentyl glycol, 1, 4-cyclohexanedimethanol, isophthalic acid, 1, 4-cyclohexanedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2-diethyl 1, 3-propanediol, 2-n-butyl-2-ethyl-1, 3-propanediol, 2-isopropyl-1, 3-propanediol, 2-di-n-butyl-1, 3-propanediol, and hexanediol. Among them, neopentyl glycol, 1, 4-cyclohexanedimethanol or isophthalic acid is preferably used. In addition, epsilon-caprolactone is also preferably used.
The resin forming the heat-shrinkable polyester film of the present invention may be added with various additives, for example, waxes, antioxidants, antistatic agents, crystal nucleating agents, viscosity reducers, heat stabilizers, coloring pigments, anti-coloring agents, ultraviolet absorbers, and the like, as required.
In the resin forming the heat-shrinkable polyester film of the present invention, fine particles as a lubricant for improving the workability (lubricity) of the film are preferably added. As the fine particles, any fine particles can be selected, and for example, as the inorganic fine particles, silica, alumina, titanium dioxide, calcium carbonate, kaolin, barium sulfate, and the like can be cited, and as the organic fine particles, acrylic resin particles, melamine resin particles, silicone resin particles, crosslinked polystyrene particles, and the like can be cited. The average particle diameter of the fine particles can be selected as needed within the range of 0.05 to 3.0 μm (in the case of measurement by Coulter counter).
The method of blending the particles with the resin for forming the heat-shrinkable polyester film may be, for example, adding the particles at any stage of the production of the polyester resin, and it is preferable to add the particles as a slurry dispersed in ethylene glycol or the like at the esterification stage or at a stage after the end of the transesterification reaction and before the start of the polycondensation reaction, thereby advancing the polycondensation reaction. Further, it is also preferable to perform the following method or the like: a method of blending a slurry of particles dispersed in ethylene glycol, water or the like with a polyester resin raw material using a kneading extruder with an exhaust port; or a method of blending the dried pellets with a polyester resin raw material using a kneading extruder.
The heat-shrinkable polyester film of the present invention may be subjected to corona treatment, coating treatment, flame treatment or the like in order to improve the adhesiveness of the film surface.
[ case of laminating films ]
In the case of a laminated film in which resin layers made of different resin compositions are laminated, it is necessary to use at least 1 polyester layer having 50 mol% or more of ethylene terephthalate units out of 100 mol% of constituent units of polyester in the laminated structure of the film. For the same reason as in the case of the single-layer film, that is, when the film structure of the laminated film has at least one layer containing 50 mol% or more of ethylene terephthalate units and the stretching ratio is made higher than 3 times, crystallization proceeds, and therefore, the attenuation rate of the shrinkage stress is small and the shrinkage stress after 30 seconds from the start of shrinkage is high.
In the present invention, when the composition has a 3-layer structure, the outermost layer (skin layer) is preferably a layer containing 50 mol% or more of ethylene terephthalate units. This is because the crystallization of the outermost layer is promoted by stretching, and the rate of attenuation of the shrinkage stress is reduced.
The composition of the resin forming the core layer is not particularly limited, and from the viewpoint of mechanical strength and the like, it is preferable that the ethylene terephthalate unit is used as a main constituent component, and the ethylene terephthalate unit is preferably 85 mol% or less out of 100 mol% of the constituent units of the polyester. When the amount of the ethylene terephthalate unit is too large, crystallization is excessively promoted, and therefore, a high shrinkage rate cannot be obtained.
Examples of the diol component of the polyester constituting the core layer include aliphatic diols such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol and hexanediol, alicyclic diols such as 1, 4-cyclohexanedimethanol, and aromatic diols such as bisphenol a.
In addition, the polyester resin contains 1 or more kinds of monomer components that can become amorphous components in 100 mol% of the polyol component or 100 mol% of the polycarboxylic acid component in the total polyester resin in a total amount of 2% or more, preferably 3% or more, more preferably 4% or more, and particularly preferably 5% or more.
Here, explanation of the term "capable of becoming an amorphous component" is described in detail.
In the present invention, the term "amorphous polymer" specifically means a polymer which does not have an endothermic peak due to melting in a measurement by a DSC differential scanning calorimeter. The amorphous polymer does not substantially undergo crystallization, cannot take a crystalline state, or has extremely low crystallinity even when crystallization is performed.
In the present invention, the term "crystalline polymer" means not the "amorphous polymer" described above, that is, a polymer having an endothermic peak due to melting in a measurement by a DSC differential scanning calorimeter. The crystalline polymer means a polymer having crystallizable properties that may crystallize at elevated temperatures of the polymer or having already crystallized.
Generally, a polymer in a state in which a plurality of monomer units are bonded is an amorphous polymer under various conditions such as low stereoregularity of the polymer, poor targeting of the polymer, large side chains of the polymer, many branches of the polymer, and small intermolecular aggregation force between the polymers. However, depending on the state of existence, crystallization proceeds sufficiently, and a crystalline polymer may be obtained. For example, even in the case of a polymer having a large side chain, crystallization proceeds sufficiently when the polymer is composed of a single monomer unit, and the polymer may be crystallized. Therefore, even in the same monomer unit, if the polymer is crystalline, the polymer may be amorphous, and therefore, the expression "unit derived from a monomer capable of becoming an amorphous component" is used in the present invention.
In the present invention, the monomer unit is a repeating unit constituting a polymer derived from 1 polyol molecule and 1 polycarboxylic acid molecule, and in the case of epsilon-caprolactone, it is a constituent unit obtained by ring-opening of a lactone ring.
When the monomer unit composed of terephthalic acid and ethylene glycol is a main monomer unit constituting the polymer, there may be mentioned a monomer unit composed of isophthalic acid and ethylene glycol, a monomer unit composed of terephthalic acid and neopentyl glycol, a monomer unit composed of terephthalic acid and 1, 4-cyclohexanedimethanol, a monomer unit composed of isophthalic acid and butanediol, and the like as the units derived from the monomer capable of becoming an amorphous component.
Examples of the monomer which can be an amorphous component of the resin forming the core layer include neopentyl glycol, 1, 4-cyclohexanedimethanol, isophthalic acid, 1, 4-cyclohexanedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2-diethyl-1, 3-propanediol, 2-n-butyl-2-ethyl-1, 3-propanediol, 2-isopropyl-1, 3-propanediol, 2-di-n-butyl-1, 3-propanediol, and hexanediol. Among them, neopentyl glycol, 1, 4-cyclohexanedimethanol or isophthalic acid is preferably used.
The total thickness of the skin layers divided by the thickness of the core layer is preferably 0.1 to 0.5. If the value obtained by dividing the total thickness of the skin layers by the thickness of the core layer is less than 0.1, the amount of the layer containing 50 mol% or more of polyethylene terephthalate units in the film composition of the laminated film is decreased, and the effect of reducing the attenuation rate of the shrinkage stress cannot be sufficiently obtained, which is not preferable. On the other hand, if the value obtained by dividing the total thickness of the skin layers by the thickness of the core layer exceeds 0.5, the core layer mainly subjected to heat shrinkage behavior becomes relatively too small, and the desired heat shrinkage ratio cannot be achieved, which is not preferable.
In the heat-shrinkable polyester film of the present invention, the core layer and the skin layer preferably have a thickness of at least 1 μm. When the thickness of the core layer or skin layer is less than 1 μm, the desired shrinkage characteristics cannot be obtained, which is not preferable.
Various additives such as waxes, antioxidants, antistatic agents, crystal nucleating agents, viscosity reducers, heat stabilizers, coloring pigments, anti-coloring agents, ultraviolet absorbers, and the like may be added to the resin forming any of the skin layer and the core layer, as required.
The multilayer film can be produced by a known method used for producing a multilayer film, and examples thereof include a feed block method and a multi-manifold method. For example, in the case of the coextrusion method, the respective resin mixtures forming the layers are melted in an extruder, merged and extruded in a T-die provided with a multi-manifold system, and stretched by a stretching device to obtain a laminated film.
The form of the laminated film is not particularly limited, and examples thereof include a laminated form having 2 kinds of 2 layer structures of A/B, 2 kinds of 3 layer structures of B/A/B, and 3 kinds of 3 layer structures of C/A/B.
[ Properties of the Heat-shrinkable polyester film of the present invention ]
When the heat-shrinkable polyester film of the present invention is treated in hot water at 98 ℃ in a no-load state for 10 seconds, the heat shrinkage rate in the longitudinal direction, which is the main shrinkage direction of the film, calculated from the length before and after shrinkage according to the following formula 1 (i.e., the hot water heat shrinkage rate at 98 ℃) is 40% to 80%.
Thermal shrinkage rate { (length before shrinkage-length after shrinkage)/length before shrinkage } × 100 (%). formula 1
When the hot water heat shrinkage rate in the longitudinal direction at 98 ℃ is less than 40%, the shrinkage amount is small when the tape is used as a bandage film, and therefore wrinkles and slackness occur in the label after heat shrinkage, which is not preferable. On the other hand, when the hot water heat shrinkage rate in the longitudinal direction at 98 ℃ is more than 80%, the container is deformed when packed in a thin and flexible beverage bottle or a container. Further, there is a problem that the adhesive portion of the cylindrical label or the band film is peeled off due to a high shrinkage stress. The hot water heat shrinkage rate in the longitudinal direction is more preferably 75% or less, and still more preferably 70% or less. The lower limit of the hot water heat shrinkage rate in the longitudinal direction at 90 ℃ is more preferably 45% or more, and still more preferably 50% or more.
When the heat-shrinkable polyester film of the present invention is treated in a hot water at 98 ℃ in a no-load state for 10 seconds, the heat shrinkage rate in the hot water in the width direction, which is a direction perpendicular to the main shrinkage direction of the film and is calculated from the length before and after shrinkage by the above formula 1, is-5% to 15%. When the hot water heat shrinkage rate in the width direction at 98 ℃ is higher than 15%, when the film is used as a band film, the length of the film in the direction perpendicular to the shrinkage direction during heat shrinkage becomes short (shrinkage cavity), and the binding force is lowered, which is not preferable because the problems such as content overflow and foreign matter mixing occur. On the other hand, if the amount is less than-5%, the label length in the direction perpendicular to the main shrinkage direction during heat shrinkage becomes long, and therefore, the label tends to be loosened and wrinkled, which is not preferable. The hot water shrinkage rate in the width direction at 98 ℃ is preferably-4% or more and 9% or less, more preferably-3% or more and 8% or less, and still more preferably-2% or more and 7% or less.
The heat-shrinkable polyester film of the present invention has a shrinkage stress ratio of 0.6 to 1.0 as shown in the following formula with respect to the shrinkage stress in the main shrinkage direction of the film measured with hot air at 90 ℃.
Shrinkage stress ratio ═ (value of shrinkage stress after 30 seconds) ÷ (maximum value of shrinkage stress)
That is, the heat-shrinkable polyester film of the present invention exhibits a specific heat-shrinkable property such that it exhibits a shrinkage stress of the same degree as the maximum heat-shrinkable stress even 30 seconds after the start of heat shrinkage. If the shrinkage stress/maximum shrinkage stress (hereinafter, stress ratio) after 30 seconds is less than 0.6, the label of the beverage bottle does not follow the shape and becomes a label without tension, and when the consumer opens the cap of the bottle while holding the bottle body, the label is rotated and is not easily opened, which is not preferable. In addition, in the case of the band-binding application of the container, there are problems that the processing of the shrink film does not become tight, the content overflows, and foreign substances are mixed in. The stress ratio is more preferably 0.75 or more, and still more preferably 0.8 or more. When the stress ratio is large, the follow-up property is good, and therefore, it is preferable, but the maximum value of the stress ratio is 1 because the shrinkage stress after 30 seconds cannot be higher than the maximum shrinkage stress.
The heat-shrinkable polyester film of the present invention has a refractive index in the longitudinal direction, which is the main shrinkage direction of the film, of 1.600 or more. If the refractive index in the longitudinal direction is less than 1.600, the film tends to wrinkle when formed into a label without stiffness (stiffness). The lower limit of the refractive index in the longitudinal direction is preferably 1.625 or more, and particularly preferably 1.650 or more. On the other hand, a refractive index in the longitudinal direction higher than 1.700 is not preferable because the solvent adhesiveness in forming a label is poor.
In the heat-shrinkable polyester film of the present invention, when the heat shrinkage stress value in the longitudinal direction, which is the main shrinkage direction of the film, is measured under the conditions of a temperature of 90 ℃, a hot air blowing rate of 5 m/sec, a test piece width of 20mm, and a chuck-to-chuck distance of 100mm, the maximum heat shrinkage stress value is preferably 15MPa or less. If the maximum thermal shrinkage stress value is 15MPa or less, the shrinkage stress is not too high, and the problem of deformation of the container when packed in a thin and flexible beverage bottle or container does not occur. Further, it is preferable that the adhesive portion of the label or the band film in a cylindrical shape is not peeled off due to high shrinkage stress. The maximum thermal shrinkage stress value is more preferably 14MPa or less, and still more preferably 12MPa or less. On the other hand, when the shrinkage stress is too small, the stress after the shrinkage process is insufficient when packaging a beverage bottle or a disposable container, and when a consumer opens a cap of the bottle while holding a bottle body, there arises a problem that the cap is not easily opened by rotating a label, and when the disposable container is used as a band, there arises a problem that contents spill out, and foreign matter is mixed in. Therefore, the maximum thermal shrinkage stress value measured by the above method is preferably 5MPa or more, and more preferably 6MPa or more.
The thickness of the heat-shrinkable polyester film of the present invention is not particularly limited, but is preferably 5 to 100 μm, more preferably 10 to 95 μm, as a heat-shrinkable film for label applications and band applications.
The heat-shrinkable polyester film of the present invention can be obtained by, for example, melt-extruding the above polyester raw material in an extruder to form an unstretched film, and stretching the unstretched film by the method described below.
When the raw material resin is melt-extruded, it is preferable to dry the polyester raw material using a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer. After drying the polyester raw material in this way, the polyester raw material is melted at a temperature of 200 to 300 ℃ by an extruder and extruded into a film. In the extrusion, any conventional method such as a T-die method or a tubular method can be used.
Then, the extruded sheet-like molten resin is quenched, whereby an unstretched film can be obtained. As a method for rapidly cooling the molten resin, the following method can be suitably employed: the molten resin is cast through a nozzle onto a rotating drum for quench solidification to provide a substantially unoriented resin sheet.
The obtained unstretched film is stretched in the longitudinal direction under predetermined conditions as described below to obtain a heat-shrinkable polyester film of the present invention. Hereinafter, the preferred stretching for obtaining the heat-shrinkable polyester film of the present invention will be described in detail in consideration of the difference from the conventional stretching method for heat-shrinkable polyester films.
[ preferred stretching method for Heat-shrinkable polyester film ]
A general heat-shrinkable polyester film is produced by stretching an unstretched film in a direction in which the film is intended to shrink. Conventionally, a heat-shrinkable polyester film that follows the shape of an object to be packaged during shrinkage and shrinks in the longitudinal direction with a tight tightness after shrinkage has been highly demanded, but a polyester film having a small shrinkage stress attenuation rate and a high shrinkage stress 30 seconds after shrinkage has started cannot be obtained by simply stretching an unstretched film in the longitudinal direction.
Therefore, a preferable stretching method of the heat shrinkable film of the present invention will be described.
As a result of investigation by the present inventors, it has been found that when the stretch ratio of a film having at least one layer containing 50 mol% or more of ethylene terephthalate units in 100 mol% of constituent units of a polyester is higher than 3 times, crystallization proceeds, and therefore, the rate of attenuation of the shrinkage stress is small, and the shrinkage stress after 30 seconds from the start of shrinkage becomes high.
In a conventional heat-shrinkable polyester film containing a large amount of amorphous component, when the film is stretched only uniaxially, the rate of attenuation of the shrinkage stress is large, and the shrinkage stress 30 seconds after the start of shrinkage is low. On the other hand, in the present invention, the shrinkage stress attenuation factor is reduced by having at least one layer containing 50 mol% or more of ethylene terephthalate units and stretching the layer at a high magnification of 3 times or more. It is considered that the attenuation of the shrinkage stress is related to crystallization by stretching. The polyester film of the present invention, which has at least one layer containing 50 mol% or more of ethylene terephthalate units and is stretched at a high ratio of 3 times or more, is likely to cause molecular crystallization. It is considered that the mobility of the molecular crystal is lower than that of the amorphous molecule when heat is applied, and that rapid relaxation of the molecular orientation is suppressed and gradual relaxation of the molecular orientation is caused when the film is thermally shrunk. That is, it is considered that the orientation is relaxed over a long period of time, and therefore, the attenuation rate of the shrinkage stress becomes low, and the shrinkage stress after 30 seconds becomes high. When a large amount of amorphous component is contained or when the stretch ratio in the longitudinal direction is less than 3 times, crystallization does not proceed so much, and therefore, it is considered that the attenuation rate of the shrinkage stress in the longitudinal direction becomes large and the shrinkage stress after 30 seconds becomes small.
From the above results, the stretching ratio in the longitudinal direction is preferably 3 times or more and 7 times or less. If the stretch ratio in the longitudinal direction is less than 3 times, crystallization of the film is insufficient and the shrinkage stress does not continue, and therefore, the film cannot sufficiently follow the shape of the packaged body. Further, the thickness variation in the longitudinal direction of the film becomes large, which is not preferable. The upper limit of the longitudinal draw ratio is not particularly limited, but is not preferable because if the ratio is more than 7, drawing in the longitudinal direction is difficult (so-called breaking is likely to occur). More preferably 3.2 times or more and 6.5 times or less, and still more preferably 3.5 times or more and 6 times or less.
The package of the present invention is formed by covering at least a part of the outer periphery of an object to be packaged with a band film (and a label) obtained from the heat-shrinkable polyester film of the present invention and heat-shrinking the film. Examples of the object to be packaged include plastic containers such as lunch boxes (various bottles including PET bottles for beverages, cans, and cakes), paper boxes, and the like. In general, when a label made of a heat-shrinkable polyester film is heat-shrunk and applied to an object to be packaged, the band film (and label) is heat-shrunk by about 5 to 70% and is tightly adhered to the package. The band film (and label) to be coated on the packaging object may be printed or may not be printed.
As a method for producing a binding film (and a label), a rectangular film is rounded in the longitudinal direction, and the ends are overlapped and bonded to form a label; alternatively, a film wound in a roll shape is rounded in the longitudinal direction of the roll, and the end portion is overlapped with the film and bonded to form a tubular body, and the obtained tubular body is cut to form a label shape. The method of bonding the films to each other can be performed by a known method such as fusion sealing, solvent bonding, bonding with a hot-melt adhesive, or bonding with an energy ray-curable adhesive.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples and can be modified as appropriate without departing from the scope of the present invention. The compositions of the raw materials used in examples and comparative examples are shown in table 1, the ratios of the mixed raw materials used in the respective layers are shown in table 2, and the production conditions and evaluation results of the films in examples and comparative examples are shown in table 3.
[ Table 1]
[ Table 2]
The evaluation method of the film is as follows.
[ Tg (glass transition Point) ]
Using a differential scanning calorimetry analyzer (DSC 220, manufactured by Seiko electronics Co., Ltd.), 5mg of an unstretched film was placed in a sample pan, and the pan was closed, and the temperature was raised from-40 ℃ to 120 ℃ at a temperature raising rate of 10 ℃/min under a nitrogen atmosphere. Tg (. degree.C.) was determined in accordance with JIS-K7121-1987.
[ Intrinsic Viscosity (IV) ]
0.2g of the polyester was dissolved in 50ml of a mixed solvent of phenol/1, 1,2, 2-tetrachloroethane (60/40 (weight ratio)), and the solution was measured at 30 ℃ with an Ostwald viscometer. The unit is dl/g.
[ Heat shrinkage ratio (Hot Water Heat shrinkage ratio) ]
The film was cut into a square of 10cm × 10cm, and was immersed in hot water at a predetermined temperature ± 0.5 ℃ for 10 seconds in a no-load state to be heat-shrunk, then immersed in water at 25 ℃ ± 0.5 ℃ for 10 seconds, pulled out of the water, and the longitudinal and transverse dimensions of the film were measured, and the heat shrinkage ratios were determined according to the following formula (1). The direction in which the thermal shrinkage rate is large is defined as the main shrinkage direction.
Heat shrinkage rate { (length before shrinkage-length after shrinkage)/length before shrinkage } × 100 (%) formula 1
[ shrinkage stress ]
A strip-like film sample having a length in the main shrinkage direction of 150mm and a width of 20mm was cut out from the heat-shrinkable film, and the shrinkage stress was measured using a Tensilon Universal tester PTM-250 (registered trademark of Orientec Co., Ltd.) with a heating furnace manufactured by Toyo Baldwin Co., Ltd. The furnace of the heating furnace of the strong elongation measuring machine was heated to 90 ℃ in advance, and the distance between chucks for fixing the film sample was set to 100 mm. When the sample was mounted on the chucks of the high elongation measuring machine, the air blowing of the heating furnace was temporarily stopped, the door of the heating furnace was opened, both ends of the sample having a length direction of 150mm were held between the chucks every 25mm, the distance between the chucks was set to 100mm, and the sample was quickly fixed so that the length direction of the chucks and the sample was aligned and the sample was horizontal. After the sample was mounted on the chuck, the door of the heating furnace was quickly closed to restart the air supply. The time when the door of the heating furnace was closed and blowing was resumed was taken as the measurement start time of the shrinkage stress, and the shrinkage stress (MPa) after 30 seconds was obtained. The maximum value of the measured value of the shrinkage stress in the period from the measurement start time of the shrinkage stress to 30 seconds after the measurement start was defined as the maximum value of the shrinkage stress (maximum shrinkage stress (MPa)). In the measurement of the shrinkage stress, the distance between chucks was fixed at 100mm, and the transition of the shrinkage stress from the start of the measurement to 30 seconds after the start of the measurement was measured. Then, the ratio of the value of the shrinkage stress from the measurement start time to the maximum value of the shrinkage stress after 30 seconds was defined as a shrinkage stress ratio (expressed by the following equation).
Shrinkage stress ratio ═ (value of shrinkage stress after 30 seconds) ÷ (maximum value of shrinkage stress)
[ refractive index ]
Each sample film was left to stand in an atmosphere of 23 ℃ and 65% RH for 2 hours or more using an Abbe refractometer 4T type manufactured by Atago K.K..
[ shrink processability (Lap Round ラップ & ラウンド) ]
A film having a width of 50mm was wound around a current plastic container (sides 150X 150mm, height 100mm) so that the body and lid portions of the container were bound with a film, and the container was sealed by fusing at 220 ℃ and then heat-shrunk to the current plastic container using a shrink tunnel having a set temperature of 90 ℃. In the evaluation of the shrinkage processability, the evaluation was performed at 4 points of wrinkle, shrinkage cavity, insufficient shrinkage, and relaxation. The number of wrinkles having a length of 5cm or more in the side direction of the container is determined in fig. 1, and the criteria are as follows.
○ is 0-4
△, 5-14
More than 15X
In the case of the shrinkage cavity, fig. 2 is a view of the shrunk band film and the container viewed from above, where L is the length from one end of one film to one end of the other film, and R is the difference between the maximum value Lmax and the minimum value Lmin when the length L is measured at 5mm intervals in the circumferential direction of the container. When R is large, the shrinkage cavity is judged to be large, and the standard is as follows.
○：0mm≤R<10mm
△:10mm≤R<15mm
×:15mm≤R
The insufficient shrinkage is judged by whether or not insufficient shrinkage occurs after the shrinkage processing, and the criterion is as follows.
○ No insufficient shrinkage
X: has insufficient contraction
The slackness was judged as a slackness if the contracted tie film was not in close contact with the container at all and no tension was generated when the tie film was touched with a hand and the film was floated, and the standard was as follows.
○ the film is tightly tightened and has no floating
X: the film is loose in processing and has floating
< preparation of polyester raw Material >
Synthesis example 1
In a stainless autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 100 mol% of dimethyl terephthalate (DMT) as a dicarboxylic acid component and 100 mol% of Ethylene Glycol (EG) as a polyol component were charged so that the ethylene glycol became 2.2 times as much as the dimethyl terephthalate in terms of a molar ratio, and 0.05 mol% of zinc acetate as an ester exchange catalyst (with respect to the acid component) and 0.225 mol% of antimony trioxide as a polycondensation catalyst (with respect to the acid component) were added to distill off the generated methanol to the outside of the system to perform an ester exchange reaction. Then, based on 280 degrees C, 26.7Pa vacuum conditions, condensation polymerization reaction, obtained the intrinsic viscosity of 0.75dl/g polyester 1. The composition is shown in table 1.
Synthesis examples 2 to 7
[ example 1]
Mixing the polyester 1, the polyester 2 and the polyester 3 in a mass ratio of 45: 5: 50 were mixed and fed into an extruder. Thereafter, the mixed resin was melted at 280 ℃, extruded from a T-die, wound around a rotating metal roll cooled to a surface temperature of 30 ℃ and quenched to obtain an unstretched film having a thickness of 42 μm. The Tg of the unstretched film was 75 ℃. The unstretched film was introduced into a longitudinal stretching machine in which a plurality of roll groups were continuously arranged, heated in a preheated roll form to a film temperature of 80 ℃, and then longitudinally stretched by a roll stretching method so that the stretching ratio in the longitudinal direction was 3.5 times and the thickness of the stretched film was 12 μm. After the longitudinal stretching, the resultant was cooled on a cooling roll having a surface temperature of 25 ℃ and then wound into a roll. The properties of the obtained film were evaluated by the above-mentioned methods. The evaluation results are shown in table 3. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ Table 3]
[ example 2]
The same operation as in example 1 was carried out except that the stretching ratio in the longitudinal direction was set to 4.5 times, and the extrusion amount of the molten mixed resin from the T-die was adjusted so that the thickness of the film stretched in the longitudinal direction became 12 μm. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 3]
The same operation as in example 1 was carried out except that the stretching ratio in the longitudinal direction was set to 5.5 times, and the extrusion amount of the molten mixed resin from the T-die was adjusted so that the thickness of the film stretched in the longitudinal direction became 12 μm. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 4]
The same operation as in example 1 was carried out except that the stretching ratio in the longitudinal direction was set to 6 times, and the extrusion amount of the molten mixed resin from the T-die was adjusted so that the thickness of the film stretched in the longitudinal direction became 12 μm. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 5 ]
Mixing the polyester 1, the polyester 2 and the polyester 3 in a mass ratio of 45: 5: 50 to form a resin mixture for the skin layer. Mixing the polyester 1, the polyester 2, the polyester 3 and the polyester 4 in a mass ratio of 25: 5: 60: 10 to form a resin mixture for the core layer. The resin mixtures for the respective layers of the skin layer and the core layer were coextruded at 280 ℃ using a 2-twin screw extruder and a T-die equipped with a 2-layer multi-manifold, and rapidly cooled with a chill roll to prepare 2-layer sheets of the skin layer/core layer. In this case, the thickness ratio of the skin layer to the core layer is defined as skin layer: core layer 2: coextrusion was carried out in the manner of 8. Subsequently, the sheet was heated to 80 ℃ and longitudinally stretched by a roll stretching method so that the stretching ratio in the longitudinal direction was 3.5 times and the total thickness of the stretched film was 12 μm. After the longitudinal stretching, the resultant was cooled by a cooling roll and then wound into a roll. The properties of the obtained film were evaluated by the above-mentioned methods. The evaluation results are shown in table 3. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 6 ]
The same operation as in example 5 was carried out except that the stretching ratio in the longitudinal direction was set to 4.5 times, and the extrusion amount of the molten mixed resin from the T-die was adjusted so that the thickness of the film stretched in the longitudinal direction became 12 μm. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 7 ]
The same operation as in example 5 was carried out except that the stretching ratio in the longitudinal direction was set to 5.5 times, and the extrusion amount of the molten mixed resin from the T-die was adjusted so that the thickness of the film stretched in the longitudinal direction became 12 μm. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 8 ]
The same operation as in example 5 was carried out except that the stretching ratio in the longitudinal direction was set to 6 times, and the extrusion amount of the molten mixed resin from the T-die was adjusted so that the thickness of the film stretched in the longitudinal direction became 12 μm. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 9 ]
Mixing the polyester 1, the polyester 2 and the polyester 3 in a mass ratio of 70: 5: 25 was mixed to form a resin mixture for a skin layer, and the procedure of example 5 was repeated. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 10 ]
The same operation as in example 9 was carried out except that the stretching ratio in the longitudinal direction was set to 4.5 times, and the extrusion amount of the molten mixed resin from the T-die was adjusted so that the thickness of the film stretched in the longitudinal direction became 12 μm. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 11 ]
The same operation as in example 9 was carried out except that the stretching ratio in the longitudinal direction was set to 5.5 times, and the extrusion amount of the molten mixed resin from the T-die was adjusted so that the thickness of the film stretched in the longitudinal direction became 12 μm. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 12 ]
The same operation as in example 9 was carried out except that the stretching ratio in the longitudinal direction was set to 6 times, and the extrusion amount of the molten mixed resin from the T-die was adjusted so that the thickness of the film stretched in the longitudinal direction became 12 μm. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 13 ]
Mixing the polyester 1, the polyester 2, the polyester 3 and the polyester 4 in a mass ratio of 5: 5: 66: 24 was mixed to form a resin mixture for a core layer, and the same procedure as in example 9 was repeated. Results of the evaluation: the film has sufficient shrinkability and good shrink processability. The evaluation results are shown in table 4.
[ example 14 ]
The same operation as in example 13 was carried out except that the stretching ratio in the longitudinal direction was set to 4.5 times, and the extrusion amount of the molten mixed resin from the T-die was adjusted so that the thickness of the film stretched in the longitudinal direction became 12 μm. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 15 ]
The same operation as in example 13 was carried out except that the stretching ratio in the longitudinal direction was set to 5.5 times, and the extrusion amount of the molten mixed resin from the T-die was adjusted so that the thickness of the film stretched in the longitudinal direction became 12 μm. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 16 ]
The same operation as in example 13 was carried out except that the stretching ratio in the longitudinal direction was set to 6 times, and the extrusion amount of the molten mixed resin from the T-die was adjusted so that the thickness of the film stretched in the longitudinal direction became 12 μm. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 17 ]
Mixing the polyester 1, the polyester 2 and the polyester 3 in a mass ratio of 45: 5: 50 to form a resin mixture for the skin layer. Mixing the polyester 1, the polyester 2, the polyester 3 and the polyester 4 in a mass ratio of 25: 5: 60: 10 to form a resin mixture for the core layer. The resin mixtures for the respective layers of the skin layer and the core layer were coextruded at 280 ℃ using a 2-twin screw extruder and a T-die equipped with a 3-layer multi-manifold, and rapidly cooled with a chill roll to produce 3-layer sheets of skin layer/core layer/skin layer. In this case, the thickness ratio of the skin layer to the core layer is defined as skin layer: core layer: skin layer 1: 8: coextrusion was carried out in the manner of 1. Subsequently, the sheet was heated to 80 ℃ and longitudinally stretched by a roll stretching method so that the stretching ratio in the longitudinal direction was 4.5 times and the total thickness of the stretched film became 12 μm. After the longitudinal stretching, the film was cooled by a cooling roll and then wound into a roll. The properties of the obtained film were evaluated by the above-mentioned methods. The evaluation results are shown in table 4. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 18 ]
Mixing the polyester 1, the polyester 2 and the polyester 3 in a mass ratio of 70: 5: 25 was conducted in the same manner as in example 17, except that the resin mixture for a skin layer was formed by mixing. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ example 19 ]
Mixing the polyester 1, the polyester 2, the polyester 3 and the polyester 4 in a mass ratio of 5: 5: 66: 24 was mixed to form a resin mixture for a core layer, and the same procedure as in example 18 was repeated. Results of the evaluation: the film has sufficient shrinkability and good shrink processability.
[ comparative example 1]
The same operation as in example 1 was carried out except that the stretching ratio in the longitudinal direction was set to 2 times, and the extrusion amount of the molten mixed resin from the T-die was adjusted so that the thickness of the film stretched in the longitudinal direction became 12 μm. Results of the evaluation: the band film after shrinkage is a film having poor shrinkage processability and having slack.
[ comparative example 2]
Mixing the polyester 1, the polyester 2 and the polyester 3 in a mass ratio of 70: 5: 25, and was charged into an extruder so that the stretching ratio in the longitudinal direction was 2.5 times, and the extrusion amount of the molten mixed resin from the T die was adjusted so that the thickness of the film after stretching in the longitudinal direction became 12 μm, in the same manner as in example 1. Results of the evaluation: the contracted binding band film has insufficient shrinkage and is a film having poor shrinkage processability.
[ comparative example 3]
Mixing the polyester 1, the polyester 2, the polyester 3 and the polyester 4 in a mass ratio of 25: 5: 60: 10 and then charged into an extruder, and the same procedure as in example 2 was repeated. Results of the evaluation: the label after shrinkage is a film having poor shrink processability, with a slack occurring therein.
[ comparative example 4]
Mixing the polyester 1, the polyester 2, the polyester 3 and the polyester 4 in a mass ratio of 5: 5: 66: 24 and charged into an extruder, and the operation was carried out in the same manner as in example 2. Results of the evaluation: the band film after shrinkage is a film having poor shrinkage processability and having slack.
[ comparative example 5 ]
The same operation as in comparative example 4 was performed except that the stretching ratio in the longitudinal direction was set to 3 times, and the extrusion amount of the molten mixed resin from the T-die was adjusted so that the thickness of the film stretched in the longitudinal direction became 12 μm. Results of the evaluation: the band film after shrinkage is a film having poor shrinkage processability and having slack.
[ Table 4]
Industrial applicability
The heat-shrinkable polyester film of the present invention has excellent properties as described above, and therefore, can be suitably used for labeling applications, binding applications such as binding bags for lunch containers, and the like. The heat-shrinkable polyester film of the present invention has a beautiful appearance as a package for bottles, lunch containers, etc. which are obtained by using the film as a label.
Claims (5)
1. A heat-shrinkable polyester film for use as a band film to be wrapped around a container and attached, the heat-shrinkable polyester film having a main shrinkage direction as a longitudinal direction, the heat-shrinkable polyester film satisfying the following characteristics (1) to (4),
(1) a hot water shrinkage ratio in the main shrinkage direction of the film when treated in hot water at 98 ℃ for 10 seconds is 40% to 80%;
(2) a hot water shrinkage ratio of-5% to 15% in a direction perpendicular to a main shrinkage direction of the film when the film is treated in hot water at 98 ℃ for 10 seconds;
(3) the shrinkage stress in the main shrinkage direction of the film measured with hot air at 90 ℃ is 0.6 to 1.0 in the shrinkage stress ratio shown by the following formula,
shrinkage stress ratio (value of shrinkage stress after 30 seconds) ÷ (maximum value of shrinkage stress);
(4) the refractive index of the film in the main shrinkage direction is 1.600 or more.
2. The heat-shrinkable polyester film of claim 1, wherein the maximum shrinkage stress in the main shrinkage direction of the film measured with hot air at 90 ℃ is 15MPa or less.
3. The heat-shrinkable polyester film according to claim 1 or 2, wherein the film comprises ethylene terephthalate as a main component, and 1 or more monomer components capable of forming an amorphous component are contained in an amount of 2 mol% or more in the entire polyester resin component.
4. The heat-shrinkable polyester film according to claim 1 or 2, wherein neopentyl glycol is used as 1 or more kinds of monomer components capable of becoming amorphous components.
5. A package obtained by coating at least a part of the outer periphery of an object to be packaged with the heat-shrinkable polyester film according to any one of claims 1 to 4 and then heat-shrinking the coated object.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015118277A JP6519331B2 (en) | 2015-06-11 | 2015-06-11 | Heat-shrinkable polyester film and package |
| JP2015-118277 | 2015-06-11 | ||
| PCT/JP2016/067049 WO2016199809A1 (en) | 2015-06-11 | 2016-06-08 | Heat-shrinkable polyester film and packaging material |
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| Publication Number | Publication Date |
|---|---|
| CN107708966A CN107708966A (en) | 2018-02-16 |
| CN107708966B true CN107708966B (en) | 2020-02-21 |
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| CN201680033264.4A Active CN107708966B (en) | 2015-06-11 | 2016-06-08 | Heat-shrinkable polyester film and package |
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| US (1) | US20180162616A1 (en) |
| JP (1) | JP6519331B2 (en) |
| KR (1) | KR102463003B1 (en) |
| CN (1) | CN107708966B (en) |
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| KR102654779B1 (en) * | 2016-11-24 | 2024-04-03 | 에스케이케미칼 주식회사 | Mdo thermoresistant heat-shrinkable multilayer film |
| KR102654778B1 (en) * | 2016-11-24 | 2024-04-03 | 에스케이케미칼 주식회사 | Mdo thermoresistant heat-shrinkable film |
| KR102261821B1 (en) | 2018-04-30 | 2021-06-08 | 에스케이씨 주식회사 | Heat shrinkable film and method for reproducing polyester container using same |
| KR102153670B1 (en) | 2018-05-21 | 2020-09-08 | 에스케이씨 주식회사 | Heat shrinkable film and preparation method thereof |
| CN113905958B (en) * | 2019-06-05 | 2023-06-06 | 东洋纺株式会社 | Heat-shrinkable polyester film having longitudinal (longitudinal) direction as main shrinkage direction |
| CN117162437B (en) * | 2023-11-02 | 2024-06-18 | 河南银金达新材料股份有限公司 | PLA heat-shrinkable film with low longitudinal shrinkage rate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1729235A (en) * | 2002-12-24 | 2006-02-01 | 东洋纺织株式会社 | Heat shrinking polyester film |
| CN104508021A (en) * | 2012-08-03 | 2015-04-08 | 东洋纺株式会社 | Heat-shrinkable polyester-based film |
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| JPS5240387B2 (en) | 1972-01-29 | 1977-10-12 | ||
| GB9806537D0 (en) * | 1998-03-26 | 1998-05-27 | Kobe Steel Europ Ltd | Polyester compositions |
| JP2004181863A (en) * | 2002-12-05 | 2004-07-02 | Toyobo Co Ltd | Heat shrinkable polyester type film roll and its manufacturing process |
| JP2007237434A (en) * | 2006-03-06 | 2007-09-20 | Teijin Dupont Films Japan Ltd | Heat-shrinkable film |
| JP4411556B2 (en) * | 2006-06-14 | 2010-02-10 | 東洋紡績株式会社 | Heat-shrinkable polyester film and method for producing the same |
| JP2011132512A (en) * | 2009-11-30 | 2011-07-07 | Sumitomo Chemical Co Ltd | Method for manufacturing liquid crystalline polyester, liquid crystalline polyester composition, reflector plate, and light-emitting device |
| JP5240387B1 (en) * | 2012-07-26 | 2013-07-17 | 東洋紡株式会社 | Heat-shrinkable polyester film and package |
| WO2014185442A1 (en) * | 2013-05-16 | 2014-11-20 | 東洋紡株式会社 | Heat-shrinkable polyester film and package |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1729235A (en) * | 2002-12-24 | 2006-02-01 | 东洋纺织株式会社 | Heat shrinking polyester film |
| CN104508021A (en) * | 2012-08-03 | 2015-04-08 | 东洋纺株式会社 | Heat-shrinkable polyester-based film |
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| US20180162616A1 (en) | 2018-06-14 |
| TWI696551B (en) | 2020-06-21 |
| WO2016199809A1 (en) | 2016-12-15 |
| KR102463003B1 (en) | 2022-11-02 |
| TW201706136A (en) | 2017-02-16 |
| JP2017213682A (en) | 2017-12-07 |
| KR20180018553A (en) | 2018-02-21 |
| CN107708966A (en) | 2018-02-16 |
| JP6519331B2 (en) | 2019-05-29 |
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